Chlorine-containing polymer vulcanizing composition

ABSTRACT

The present invention provides a chlorine-containing polymer vulcanizing composition with improved preservation stability. The present invention is a chlorine-containing polymer vulcanizing composition obtained by blending (a) a zeolite compound, (b) a vulcanizing agent, and (c) an optional organic vulcanization accelerator. The zeolite compound can be natural zeolite, an A-type, X-type, or Y-type synthetic zeolite, a sodalite, natural or synthetic mordenite, ZSM-5, or a metal substitution product thereof. The zeolite compound is preferably an activated zeolite compound. With respect to 100 parts by weight of chlorinated polyethylene, (a) preferably 0.5 to 30 parts by weight, more preferably 5 to 25 parts by weight, of the zeolite compound, (b) preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, of the vulcanizing agent, and (c) preferably 0.5 to 3 mol, more preferably 0.7 to 1.5 mol, of the vulcanization accelerator with respect to 1 mol of (b) the vulcanizing agent are blended.

This application is a Continuation of prior application Ser. No.09/329,334 filed Jun. 10, 1999 now U.S. Pat. No. 6,500,884 which ishereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a chlorine-containing polymervulcanizing composition such as represented by chlorinated polyethyleneor epichlorohydrin polymer, and to a vulcanized product thereof.

2. Description of the Prior Art

Generally, a chlorine-containing polymer is widely used as a materialfor a rubber product or a resin product, or as a material for anadhesive or a paint because of its excellent heat resistance, oilresistance, weather resistance, ozone resistance, and abrasionresistance. In particular, chlorinated polyethylene is attractingpeople's attention as a rubber material utilizing its excellent heatresistance, oil resistance, weather resistance, and ozone resistance.

Various proposals have already been made for vulcanization ofchlorinated polyethylene. For example, organic peroxides and varioussulphur-containing compounds such as mercaptotriazines are proposed as avulcanizing agent for chlorinated polyethylene. It is also known to usevarious organic vulcanization accelerators such as an amine compound incombination with the vulcanizing agent for accelerating vulcanization ofchlorinated polyethylene. It is a common knowledge of those skilled inthe art that an acid receiving agent must be blended with a vulcanizingcomposition for absorbing an acid component generated in a small amountin vulcanizing chlorinated polyethylene. For example, Japanese Laid-openPatent Publication No. 55-39250/1980 proposes a metal compound selectedfrom the group consisting of oxide, hydroxide, carboxylate, silicate,carbonate, phosphite, borate, basic sulfite and tribasic sulfate of agroup IVA metal in the periodic table, as the acid receiving agent.

A vulcanizing composition disclosed in Japanese Laid-open PatentPublication 63-28047/1988 provides stability of a vulcanized product anda suitable vulcanization speed, and the patent publication gives oxide,hydroxide, carboxylate, silicate, carbonate, phosphite and borate of agroup II metal in the periodic table, and oxide, basic phosphite, basiccarbonate, basic carboxylate, basic sulfite, and tribasic sulfate of agroup IVA metal in the periodic table as example of the metal compounds.Specific examples thereof include magnesia, magnesium hydroxide, bariumhydroxide, magnesium carbonate, barium carbonate, slaked lime, quicklime, calcium carbonate, calcium silicate, calcium stearate, zincstearate, calcium phthalate, magnesium phosphite, calcium phosphite,zinc white, tin oxide, litharge, red lead, white lead, dibasic leadphthalate, dibasic lead carbonate, tin stearate, basic lead phosphite,basic tin phosphite, basic lead sulfite and tribasic lead sulfate.

Japanese Laid-open Patent Publication 53-3439/1978, 54-58750/1979,09-176433/1997, and others disclose a vulcanizing composition containinga thiadiazole compound as a vulcanizing agent for a chlorine-containingpolymer, in which a basic metal oxide, a basic metal salt, a basic metalhydroxide, or the like is used as a compounding agent.

However, none of these vulcanizing compositions is a compositionobtained by blending a zeolite compound as an acid receiving agent witha chlorine-containing polymer. Although these vulcanizing compositionsprovide vulcanized products having good vulcanization properties and areput into industrial use, they have a poor preservation stability andinvolves various restrictions in industrial rubber processing. Forexample, if the preservation stability of the vulcanizing composition ispoor, vulcanization proceeds during preservation to make vulcanizationmolding impossible, whereby the vulcanizing composition must bediscarded, desired vulcanization properties can not be obtained, or adimension precision is greatly reduced, even though the vulcanizationmolding can be carried out.

Japanese Laid-open Patent Publication 58-18939/1983 discloses blending aspecific aluminosilicate as a heat stabilizer with a chlorine-containingpolymer. However, this does not contain a vulcanizing agent, i.e. is notone obtained by blending an aluminosilicate with a vulcanizingcomposition, much less gives a teaching of preservation stability of thevulcanizing composition.

Japanese Laid-open Patent Publications 07-157566/1995 and 07-286098/1995disclose a polymer vulcanizing composition containing an epichlorohydrinpolymer, a mercapto vulcanizing agent, and a hydrotalcite. However, thisvulcanizing composition is not one obtained by blending a zeolitecompound as an acid receiving agent.

Japanese Laid-open Patent Application 60-233138/1985 discloses acomposition containing a chlorosulfonated polyolefin, an epoxy compound,and an A-type zeolite. However, this is a disclosure that the A-typezeolite preserves a white color of the chlorosulfonated polyolefin atthe time of heating and increases the strength of the vulcanizedproduct, and it also fails to give a teaching on the preservationstability of the vulcanizing composition.

SUMMARY OF THE INVENTION

In view of the above-mentioned circumstances, the object of the presentinvention is to provide a chlorine-containing polymer vulcanizingcomposition with improved preservation stability.

The inventors of the present invention have made various studies inorder to solve the above problems, and found out that blending a zeolitecompound as an acid receiving agent is effective in improving thepreservation stability of a chlorine-containing polymer vulcanizingcomposition, thereby completing the present invention.

Accordingly, the present invention provides a chlorine-containingpolymer vulcanizing composition obtained by blending with achlorine-containing polymer, (a) a zeolite compound, (b) a vulcanizingagent, and (c) an optional organic vulcanization accelerator.

Further, the present invention provides a chlorine-containing polymervulcanizing composition containing (d) an optional inorganicvulcanization accelerator in addition to the above-mentioned compoundingagents (a), (b), and (c). By blending the (d) component, thevulcanization speed and the compression set can be improved.

DETAILED DESCRIPTION OF THE INVENTION

The term “chlorine-containing polymer” as a major component of thecomposition is used to include a polymer with chlorine directly bondedto a main chain of the polymer or a polymer obtained using achlorine-containing monomer as a main constituent element, such aschlorinated polyethylene, an epichlorohydrin polymer, polyvinylchloride, chloroprene rubber, chlorinated natural rubber orchlorosulfonated polyethylene; a polymer containing a small amount ofchlorine as a cross-linking point, such as chlorinated butyl rubber; anacrylic rubber obtained by copolymerizing an acrylic monomer with achlorine-containing monomer; and others.

These polymers can be each a commercially available product, and can beused without special limitation.

Among the above chlorine-containing polymers, chlorinated polyethyleneis obtained by chlorinating polyethylene powder or particles in anaqueous suspension or in an organic solvent. In the present invention,chlorinated polyethylene is preferably obtained by chlorination in anaqueous suspension. The polyethylene to be used as a raw material is ahomopolymer of ethylene or a copolymer of ethylene with a copolymerablecomonomer. Examples of the comonomers include α-olefins such aspropylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and4-methyl-pentene-1; acetates such as vinyl acetate and ethyl acetate;(meth)acrylic acid; and (meth)acrylic acid esters such as methyl(meth)acrylate and ethyl (meth)acrylate. The polyethylene has aweight-average molecular weight of preferably 40,000 to 700,000, morepreferably 50,000 to 300,000.

The polyethylene to be used as a raw material can be a high densitypolyethylene and a blend of a high density polyethylene with a lowdensity polyethylene.

The chlorine content of chlorinated polyethylene to be used in thepresent invention is preferably 20 to 50% by weight, more preferably 25to 45% by weight, when the vulcanized product is to be used as avulcanized rubber. If the chlorine content is too high or too low, thehardness of the composition to be obtained can be too high. An amorphousor substantially amorphous chlorinated polyethylene is preferable. Ifthe vulcanized product is to be used as a vulcanized adhesive for rubberand metal, the chlorine content of the chlorinated polyethylene to beused in the present invention is preferably 50 to 75% by weight, morepreferably 60 to 70% by weight. If the chlorine content is 50% by weightor lower, the adhesive power can be insufficient, whereas if the contentis 75% by weight or higher, the chlorination takes a lot of time, sothat it is not preferable.

Among the above chlorine-containing polymers, the epichlorohydrinpolymer is a homopolymer of epichlorohydrin or a copolymer ofepichlorohydrin with a copolymerable epoxide such as ethylene oxide,propylene oxide or allyl glycidyl ether. Examples of the epichlorohydrinpolymers include epichlorohydrin homopolymer, epichlorohydrin-ethyleneoxide copolymer, epichlorohydrin-propylene oxide copolymer,epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer andepichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ethertetrapolymer. Among these, preferred polymers are epichlorohydrinhomopolymer, epichlorohydrin-ethylene oxide copolymer andepichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. Morepreferred polymers are epichlorohydrin-ethylene oxide copolymer andepichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. In thesecopolymers, it is preferable that an epichlorohydrin component iscontained at least at 10 mol % in view of ensuring a practicalvulcanization speed.

The molecular weight of the epichlorohydrin polymer is preferably ML₁₊₄(100° C.)=about 30 to 150 typically in Mooney viscosity representation.

The chlorine content in the chlorosulfonated polyethylene to be used inthe present invention is preferably 20 to 50% by weight, more preferably25 to 45% by weight when it is to be used as a vulcanized rubber. If thechlorine content is too high or too low, the hardness of the obtainedvulcanized rubber can be too high. The amount of the chlorosulfone groupintroduced as a vulcanizing point is preferably 1 to 2% by weightgenerally in terms of sulphur content. Usually, chlorosulfonatedpolyethylene having a molecular weight of ML₁₊₄ (100° C.)=about 20 to150 in Mooney viscosity representation is used as it is. An amorphous orsubstantially amorphous chlorosulfonated polyethylene is preferable.

The chlorine-containing polymer can be a blend of a chlorine-containingpolymer in a major proportion and another rubber and/or resin in a minorproportion. For example, the chlorinated polyethylene can be oneobtained by blending a nitrile rubber, an acrylic rubber, or the likewith chlorinated polyethylene. This blending is carried out for thepurpose of improving oil resistance, heat resistance and others.

The zeolite compound (a) acts as an acid receiving agent, and greatlyimproves the preservation stability of the chlorine-containing polymervulcanizing composition. This effect produced by using a zeolitecompound as an acid receiving agent is unexpected and surprising.

The zeolite compound of the composition can be various kinds of zeolite,such as a natural zeolite, an A-type, X-type, or Y-type syntheticzeolite, a sodalite, a natural or synthetic mordenite, ZSM-5, or a metalsubstitution product thereof. These can be used either alone or inmixtures thereof. The metal in the metal substitution product is oftensodium. It is preferable to use a zeolite compound which has a high acidreceiving capability.

The method for producing synthetic zeolite is known. For example, in thehydrothermal synthesis method, oxide (base) of an alkali or alkali earthmetal, alumina, silica, and water are used as starting materials, andthese are allowed to react typically at a temperature of 100° C. ormore, followed by precipitation of a zeolite crystal. It is possible touse a natural silicate mineral, for example, kaoline or clay such asallophene, or a volcanic glass as a starting material. For example,Japanese Examined Patent Publication 26-1119/51 discloses a method inwhich an active silicic acid obtained by treating an acid clay(montmorillonite) with an acid is allowed to react with a dilute sodiumaluminate to produce a synthetic zeolite.

As the zeolite compound, it is preferable to use an activated zeolitecompound. The term “activated zeolite compound” stands for one which issubstantially free from water. Such activation can be carried out byheating to dehydrate a zeolite compound at a temperature of 100° C. ormore in a dried air or nitrogen stream, or by introducing a zeolitecompound at the time of kneading a chlorine-containing polymer withother components and exposing the resulting mixture to a kneadingtemperature of 140° C. to 200° C.

The vulcanizing agent is not specifically limited, and can be sulphur, amercaptotriazine compound, a thiadiazole compound,2,3-dimercaptoquinoxaline derivative, a thiourea compound, an amine, athiuram compound, or the like.

The vulcanizing agent for chlorinated polyethylene is preferably amercaptotriazine compound or a thiadiazole compound.

The mercaptotriazine compound can be a compound represented by thefollowing general formula (I).

In the formula (I), R is a group selected from the group consisting of amercapto group, an alkoxy group, an alkylamino group, a dialkylaminogroup, a cycloalkylamino group, a dicycloalkylamino group and anarylamino group.

Specific examples of the mercaptotriazine compounds include2,4,6-trimercapto-1,3,5-triazine, 1-methoxy-3,5-dimercaptotriazine,1-hexylamino-3,5-dimercaptotriazine,1-diethylamino-3,5-dimercaptotriazine,1-cyclohexylamino-3,5-dimercaptotriazine,1-dibutylamino-3,5-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine,1-phenylamino-3,5-dimercaptotriazine.

The thiadiazole compound can be a compound represented by the followinggeneral formula (II), (III), (IV), or (V).

In the formulae (II) and (III), R₁ and R₂ are identical or different,and represent a hydrogen atom, a group —(C═O)R₃, or a group —R₄OR₅,wherein R₃ is an alkyl group having 1 to 17 carbon atoms, an aryl grouphaving one or two ring(s), an acyl group having 7 to 14 carbon atoms, anaralkyl group having 7 to 8 carbon atoms, or a cyclohexyl group; and R₄and R₅ are identical or different, and represent an alkyl group having 1to 8 carbon atoms.

In the formulae (IV) and (V), R₆ and R₇ are identical or different, andrepresent an alkyl group having 1 to 8 carbon atoms; R₈ and R₉ areidentical or different, and represent a hydrogen atom or an alkyl grouphaving 1 to 8 carbon atoms; n is 1 or 2; and X is an oxygen atom or asulphur atom.

Specific examples of the thiadiazole compounds include2,5-dimercapto-1,3,4-thiadiazole, a monobenzoate derivative of2,5-dimercapto-1,3,4-thiadiazole, and a dibenzoate derivative of2,5-dimercapto-1,3,4-thiadiazole, and preferred examples are2,5-dimercapto-1,3,4-thiadiazole,5-mercapto-1,3,4-thiadiazole-2-thiobenzoate,1,3,4-thiadiazolyl-2,5-dithiobenzoate,5-mercapto-1,3,4-thiadiazole-2-thiostearate,5-mercapto-1,3,4-thiadiazole-2-thio-1-naphthoate,5-mercapto-1,3,4-thiadiazole-2-thiophenylacetate,5-mercapto-1,3,4-thiadiazole-2-thiocyclohexylcarboxylate,5-mercapto-1,3,4-thiadiazole-2-thio-p-toluate,5-mercapto-1,3,4-thiadiazole-2-thiocinnamate,2,5-di(butoxymethyl)-1,3,4-thiadiazole,2,2′-dimercapto-5,5′-dithiobis(1,3,4-thiadiazole),2,2′-di(butoxymethyl)-5,5′-dithiobis(1,3,4-thiadiazole), and the like.

Preferred examples of the vulcanizing agents for epichlorohydrinpolymers include 2,3-dimercaptoquinoxaline derivatives and thioureacompounds in addition to the above-mentioned mercaptotriazine compoundsand thiadiazole compounds.

Examples of the 2,3-dimercaptoquinoxaline derivatives includequinoxaline-2,3-dithiocarbonate,6-methylquinoxaline-2,3-dithiocarbonate,6-isopropylquinoxaline-2,3-dithiocarbonate,5,8-dimethylquinoxaline-2,3-dithiocarbonate, and the like.

The thiourea compounds can be thiourea compounds such as anethylenethiourea compound, a dialkylthiourea compound, and atrialkylthiourea compound. Specific examples thereof include2-mercaptoimidazoline, 1,3-diethylthiourea, 1,3-dibutylthiourea,trimethylthiourea and the like.

The vulcanizing agent for a chlorosulfonated polyethylene can be athiuram compound. A specific example thereof is dipentamethylenethiuramtetrasulfide.

These vulcanizing agents can be used either singly or in combination oftwo or more.

The organic vulcanization accelerator (c) can be a member selected fromthe group consisting of a primary amine, a secondary amine, a tertiaryamine, an organic acid salt or adduct of said amine, an aldehyde-ammoniacompound, an aldehyde-amine compound, a guanidine compound, a thiazolecompound, a sulfeneamide compound, a thiuram compound, dithiocarbamicacid compound, 1,8-diazabicyclo(5,4,0)undecene-7 and a weak acid saltthereof, a quaternary ammonium salt compound and mixtures of two or morethereof. However, the vulcanizing agent is not limited thereto.

The primary amine, the secondary amine, and the tertiary amine arepreferably an aliphatic or alicyclic amine having 5 to 20 carbon atoms.Examples of preferred amine include n-hexylamine, octylamine,dibutylamine, tributylamine, trioctylamine, di(2-ethylhexyl)amine,dicyclohexylamine, hexamethylenediamine, and the like.

The organic acid that forms a salt with the above-mentioned amine can bea carboxylic acid, a carbamic acid, 2-mercaptobenzothiazole,dithiophosphoric acid and the like. The substance that forms an additionproduct with the above-mentioned amine can be an alcohol or an oxime.Specific examples of the organic acid salt or the addition product ofamine include n-butylamine acetate; dibutylamine oleate,hexamethylenediamine carbamate, a dicyclohexylamine salt of2-mercaptobenzothiazole and the like.

Examples of the aldehyde-ammonia accelerator includehexamethylenetetramine, a reaction product of acetaldehyde and ammonia,and the like.

The aldehyde-amine accelerator can be, for example, a condensate of anamine with at least one aldehyde having 1 to 7 carbon atoms. Examples ofpreferred amine can be, for example, aniline, butylamine and the like.Among these, a condensate of aniline with an aldehyde having 1 to 7carbon atoms is preferable. Specific examples thereof include acondensate aniline with butyraldehyde, a condensate of aniline withheptaldehyde, a condensate of aniline with acetaldehyde andbutyraldehyde.

The guanidine accelerator can be diaryl guanidine such asdiphenylguanidine, ditolylguanidine or the like.

The thiazole accelerator can be, for example, 2-mercaptobenzothiazole,dibenzothiazyl disulfide, a zinc salt of 2-mercaptobenzothiazole or thelike.

The sulfeneamide accelerator comprises a 2-benzothiazylsulfeneamide of aprimary amine or a secondary amine represented by the general formula(VI).

In the formula (VI), R₁₀ and R₁₁ are identical or different, andrepresent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, acycloalkyl group having 1 to 12 carbon atoms, or an aralkyl group having1 to 12 carbon atoms, excluding the case where R₁₀ and R₁₁ are both ahydrogen atom. R₁₀ and R₁₁ can be bonded to form a ring via or not viahetero atom(s).

Examples of the primary amine or the secondary amine that forms asulfeneamide include cyclohexylamine, butylamines, diethylamine,dipropylamines, dioctylamines, dilaurylamines, dicyclohexylamine,piperidine, pipecoline, morpholine, and piperazine.

Specific examples of the sulfeneamide organic vulcanization acceleratorsinclude N-ethyl-2-benzothiazylsulfeneamide,N-t-butyl-2-benzothiazylsulfeneamide,N,N-di-isopropyl-2-benzothiazylsulfeneamide,N,N-di-n-butyl-2-benzothiazylsulfeneamide,N,N-di-cyclohexyl-2-benzothiazylsulfeneamide,N-oxy-diethylene-2-benzothiazylsulfeneamide and the like.

The thiuram accelerator comprises a thiuram sulfide compound representedby the following general formula (VII).

In the formula (VII), R₁₂ and R₁₃, R₁₄ and R₁₅ are identical ordifferent, and represent, for example, an alkyl group, an aryl group, acycloalkyl group, or an aralkyl group. R₁₂ and R₁₃ and/or R₁₄ and R₁₅can be bonded each other to form a ring via or not via hetero atom(s).

Specific examples of the thiuram accelerators include tetramethylthiuramdisulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide,tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide andthe like.

The dithiocarbamic acid accelerator is exemplified by piperidinepentamethylenedithiocarbamate, zinc dimethyldithiocarbamate, copperdimethylcarbamate or the like.

The above-mentioned accelerator can be in a form of predispersion in aninorganic filler, an oil, a polymer or the like.

The compound 1,8-diazabicyclo(5,4,0)-undecene-7 (hereafter referred toas DBU) is a compound represented by the following formula (VIII).

The weak acid salt of DBU can be a carbonate, a carboxylate, a salt witha phenolic substance, a salt with an enolic substance, a salt with athiol or the like. Examples of the acids that constitute these saltsinclude carbonic acid, acetic acid, formic acid, sorbic acid, salicylicacid, β-oxynaphthoic acid, phenol, phthalic acid, cyanuric acid,mercaptobenzothiazole, mercaptobenzoimidazole, and phenolic resins,phenol novolak resins and the like.

Also, it is possible to use DBU by dissolving it into a liquid substancesuch as a higher alcohol or a glycol; to use DBU in a powder state bydispersing it in an inorganic filler; or to use DBU in a sheet-like orpellet-like form by incorporating it into a polymer substance.

The quaternary ammonium salt compound to be used as the organicvulcanization accelerator is a compound represented by the followinggeneral formula (IX).

In the formula (IX), R₁₆, R₁₇, R₁₈, and R₁₉ are identical or different,and represent a group selected from an alkyl group having 1 to 17 carbonatoms, a cyclohexyl group, a phenyl group, and a benzyl group. Examplesof the above alkyl group having 1 to 17 carbon atoms include methyl,propyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl and thelike. X is an anion and can be, for example, a halide anion such asfluoride ion, bromide ion, chloride ion or iodine ion.

These organic vulcanization accelerators may be used either singly or incombination of two or more.

The inorganic vulcanization accelerator (d) can be a compound selectedfrom the group consisting of a basic metal oxide, a basic metal salt, abasic metal hydroxide, a basic silicon dioxide, a silicate, and ahydrotalcite. However, the inorganic vulcanization accelerator (d) isnot limited thereto.

Specific examples of the inorganic vulcanization accelerator (d) includemagnesium oxide, calcium oxide, aluminum oxide, magnesium hydroxide,calcium hydroxide, aluminum hydroxide, calcium carbonate, basic silicondioxide, calcium silicate, synthetic hydrotalcite and the like. Theinorganic vulcanization accelerator is suitably selected in accordancewith the other compounding agents.

Making much of preservation stability of the composition, it ispreferable to use a basic metal carbonate. The inorganic vulcanizationaccelerator can be surface-treated before use.

The inorganic vulcanization accelerator is added preferably at 0 to 20parts by weight. If it is added at more than 20 parts by weight, theaccelerator does not exhibit an increased effect and merely exhibits aneffect as a filler.

A polyvalent hydroxyl compound can be added in order to adjust thevulcanization speed. Such a polyvalent hydroxyl compound can be, forexample, a trivalent to hexavalent alcohol such as glycerin, ethyleneglycol, sorbit, trimethylolpropane or trimethylolethane, but is notlimited thereto.

It is also possible to use the above-mentioned inorganic vulcanizationaccelerator as an additive which is generally called a “filler” in therubber industry.

One suitable embodiment of the present invention is achlorine-containing polymer vulcanizing composition obtained byblending, with a chlorine-containing polymer, (a) a zeolite compound,(b) a vulcanizing agent, and (c) an organic vulcanization acceleratorcomprising a member selected from the group consisting of a primaryamine, a secondary amine, a tertiary amine, an organic acid salt oradduct thereof, an aldehyde-ammonia accelerator, an aldehyde-amineaccelerator, a guanidine accelerator, a thiazole accelerator, asulfeneamide accelerator, a thiuram accelerator, dithiocarbamic acidaccelerator, DBU and a weak acid salt thereof, a quaternary ammoniumsalt compound and mixtures of two or more thereof.

A vulcanizing composition in which the above chlorine-containing polymeris a chlorinated polyethylene, an epichlorohydrin polymer, or achlorosulfonated polyethylene is especially preferable.

The contents of the components in the chlorine-containing polymervulcanizing composition is such that, with respect to 100 parts byweight of the chlorine-containing polymer, (a) preferably 0.5 to 30parts by weight, more preferably 5 to 25 parts by weight, of the zeolitecompound, (b) preferably 0.1 to 5 parts by weight, more preferably 0.5to 3 parts by weight, of the vulcanizing agent, and (c) preferably 0.5to 3 mol, more preferably 0.7 to 1.5 mol, of the organic vulcanizationaccelerator with respect to 1 mol of the vulcanizing agent are blended.

Another suitable embodiment of the present invention is achlorine-containing polymer vulcanizing composition obtained byblending, with a chlorine-containing polymer, (a) a zeolite compound,(b) a thiadiazole compound, and (c) an organic vulcanization acceleratorcomprising a member selected from the group consisting of a primaryamine, a secondary amine, a tertiary amine, an organic acid salt oradduct thereof, an aldehyde-ammonia accelerator, an aldehyde-amineaccelerator, a guanidine accelerator, a thiazole accelerator, asulfeneamide accelerator, a thiuram accelerator, dithiocarbamic acidaccelerator, DBU and a weak acid salt thereof, a quaternary ammoniumsalt compound and mixtures of two or more thereof, and (d) a compoundselected from the group consisting of a basic metal oxide, a basic metalsalt, a basic silicon dioxide, a silicate and a hydrotalcite.

A vulcanizing composition in which the above chlorine-containing polymeris chlorinated polyethylene or an epichlorohydrin polymer is especiallypreferable.

The contents of the components in the chlorine-containing polymervulcanizing composition is such that, with respect to 100 parts byweight of the chlorine-containing polymer, (a) preferably 0.5 to 30parts by weight, more preferably 5 to 25 parts by weight, of the zeolitecompound, (b) preferably 0.1 to 5 parts by weight, more preferably 0.5to 3 parts by weight, of the vulcanizing agent, (c) preferably 0.5 to 3mol, more preferably 0.7 to 1.5 mol, of the organic vulcanizationaccelerator with respect to 1 mol of the vulcanizing agent, and (d)preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts byweight, of the inorganic vulcanization accelerator are blended.

A vulcanized product having good vulcanization properties can beobtained by vulcanizing the above chlorine-containing polymervulcanizing composition.

In the present specification, “good preservation stability” means thatthe difference (hereafter referred to as ΔVm) between the Vm value (thelowest Mooney viscosity) of the vulcanizing composition immediatelyafter the kneading in the Mooney Scorch test as defined by JIS (JapaneseIndustrial Standard) K6300 (physical test method for unvulcanizedrubber) and the Vm value of the composition in the Mooney Scorch test asmeasured after it was left to stand for 3 or 7 days at 35° C. underhumidity of 75% after the kneading, is small.

The tensile physical property (hereafter referred to as initial physicalproperties) was measured according to JIS K6251, and the compression setwas measured according to JIS K6262.

Into the vulcanizing composition of the present invention may be addedvarious additives generally used in the field of the art, for example, afiller, a reinforcing agent, a plasticizer, a stabilizer, an anti-agingagent, a lubricant, a viscosity-imparting agent, a pigment, aflame-retardant, an ultraviolet absorber, a foaming agent, avulcanization moderator, and the like, if necessary. A short fiber orthe like can be added to improve the strength and the rigidity.

In order to prepare the vulcanizing composition of the presentinvention, the above compounding agents are kneaded by means of anordinary mixing roll, a Banbury mixer, a twin-screw kneading extruder,or the like kneader, and the kneaded product is then formed into adesired sheet-like shape by means of an oven roll or the like. Themolding or the vulcanization is carried out by means of a pressingmachine, an extruder, an injection-molding machine or the like to give arubber product having a desired shape. The vulcanization condition issuitably selected within the range of 100 to 200° C. and several minutesto two hours.

A laminated product and a laminated hose having a layer of the abovevulcanizing composition can be prepared applying a well-known generallamination process or an extrusion-molding technique. For example, thelaminated product can be obtained by laminating the layer of the abovevulcanizing composition directly on a layer made of epichlorohydrinrubber, nitrile rubber, nitrile rubber having polyvinyl chloride blendedtherewith, or acrylic rubber, followed by vulcanizing the composition.Also, the laminated hose can be obtained by molding a hose including aninner layer made of epichlorohydrin rubber, nitrile rubber, nitrilerubber having polyvinyl chloride blended therewith, or acrylic rubber,and an outer layer made of the above vulcanizing composition, followedby vulcanizing the composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Specific embodiments for practicing the present invention will bedescribed with reference to the following Examples. However, the presentinvention is not limited by the following Examples unless it departsfrom the spirit and scope of the present invention.

The details of the compounding agents used in the Examples andComparative Examples are as follows.

Chlorinated polyethylene; “DAISOLAC H-135” manufactured by DAISO CO.,LTD., with a chlorine content of 35%

Epichlorohydrin polymer; ethylene/epichlorohydrin copolymer, “EPICHLOMERC” manufactured by DAISO CO., LTD., with a chlorine content of 25%

Chlorosulfonated polyethylene; “HYPALON 40” manufactured by DuPont DowElastomers

NBR/PVC: “NV75” manufactured by JSR Corporation, a blended product ofNBR/PVC=70/30

Reinforcing agent; FEF carbon black, “SEAST SO” manufactured by TokaiCarbon Co., Ltd.

Plasticizer I; diisodecyl adipate, “DIDA” manufactured by DaihachiChemical Industry Co., Ltd.

Plasticizer II; “ADEKACIZER RS107” manufactured by Asahi Denka Kogyo K.K.

Plasticizer III; dioctyl phthalate

Lubricant; sorbitan monostearate, “SPLENDER R300” manufactured by KaoCorporation

Acid receiving agent I; synthetic zeolite (I), A-type zeolite,“MIZUKALIZER DS” manufactured by Mizusawa Industrial Chemicals, Ltd.

Acid receiving agent II; synthetic zeolite (II), X-type zeolite,“Molecular Sieves 13X” manufactured by Wako Pure Chemical Industries,Ltd.

Acid receiving agent III; highly active magnesium oxide, “MgO#150”manufactured by Kyowa Chemical Industry Co., Ltd.

Vulcanizing agent I; 2,4,6-trimercapto-1,3,5-triazine

Vulcanizing agent II; 2-anilino-4,6-dimercaptotriazine

Vulcanizing agent III; 2,5-dimercapto-1,3,4-thiadiazole

Vulcanizing agent IV; 2,2′-dimercapto-5,5′-dithiobis(1,3,4-thiadiazole)

Vulcanizing agent V;2,2′-di(butoxymethyl)-5,5′-dithiobis(1,3,4-thiadiazole)

Vulcanizing agent VI; dipentamethylenethiuram tetrasulfide

Vulcanizing agent VII; 6-methylquinoxaline-2,3-dithiocarbonate

Organic vulcanization accelerator I; dicyclohexylamine salt of2-mercaptobenzothiazole

Organic vulcanization accelerator II; dibutylamine

Organic vulcanization accelerator III; condensate of n-butyraldehydewith aniline, “NOCCELER 8” manufactured by Ouchi-Shinko ChemicalIndustrial Co., Ltd.

Organic vulcanization accelerator IV;N.N-dicyclohexyl-2-benzothiazolylsulfeneamide, “NOCCELER DZ”manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd.

Organic vulcanization accelerator V; tetrabutylammonium chloride

Organic vulcanization accelerator VI; tetramethylthiuram disulfide,“NOCCELER TT” manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd.

Organic vulcanization accelerator VII;N-cyclohexyl-2-benzothiazolylsulfeneamide, “NOCCELER CZ” manufactured byOuchi-Shinko Chemical Industrial Co., Ltd.

Organic vulcanization accelerator VIII; a salt of DBU and a phenolicresin, “P-152” manufactured by DAISO CO., LTD.

Organic vulcanization accelerator IX; dibenzothiazyl disulfide,“NOCCELER DM” manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd.

Organic vulcanization accelerator X; tetramethylthiuram monosulfide,“NOCCELER TS” manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd.

Inorganic vulcanization accelerator I; calcium carbonate, “HAKUENKA O”manufactured by Shiraishi Kogyo Kaisha, Ltd.

Inorganic vulcanization accelerator II; resin acid-treated calciumcarbonate, “HAKUENKA CC” manufactured by Shiraishi Kogyo Kaisha, Ltd.

Inorganic vulcanization accelerator III; light calcium carbonate,“SILVER W” manufactured by Shiraishi Kogyo Kaisha, Ltd.

Inorganic vulcanization accelerator IV; calcium silicate, “SOLEX CM”manufactured by TOKUYAMA CORPORATION

Inorganic vulcanization accelerator V; white filler, basic silicondioxide (pH=10), “CARPLEX #1120” manufactured by Shionogi & Co., Ltd.

White filler I; magnesium silicate, “MISTRON VAPOR TALC” manufactured byNihon Mistron Co., Ltd.

White filler II; magnesium silicate, “HIGH TORON” manufactured byTAKEHARA KAGAKUKOGYO Co., Ltd.

White filler III; anhydrous aluminum silicate, “ICE BERG” manufacturedby Burgess Pigment Company

Anti-aging agent; nickel dibutyldithiocarbamate, “NOCRAC NBC”manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd.

White carbon: “Nip SIL VN-3” manufactured by Nippon Silica IndustrialCo., Ltd.

Light calcium carbonate: “AKADAMA” manufactured by Shiraishi KogyoKaisha, Ltd.

Calcium hydroxide: “CARBIT” manufactured by Ohmi Chemical Industry Co.,Ltd.

Anti-scorching agent: N-(cyclohexylthio)phthalimide, “PVI” manufacturedby Monsanto Japan, Ltd.

EXAMPLE 1

Referring to Table 1, to 100 parts by weight of chlorinated polyethylenewere added 60 parts by weight of carbon black as a reinforcing agent and30 parts by weight of diisodecyl adipate as a plasticizer, followed bykneading the resulting mixture at 130° C. for 6 minutes in a kneader.Then, 2 parts by weight of synthetic zeolite (I) as an acid receivingagent, 1.25 parts by weight of 2,4,6-trimercapto-1,3,5-triazine as avulcanizing agent, and 2.5 parts by weight of dicyclohexylamine salt of2-mercaptobenzothiazole as an organic vulcanization accelerator wereadded to the above kneaded product, followed by further kneading theproduct by means of a roll heated to 70 to 80° C. to produce asheet-like rubber composition having a thickness of 2 to 3 mm forvulcanization. This rubber composition was put into a mold of 15×15 cmand heated at 160° C. at 100 kg/cm² for 15 minutes in a pressing machineto give a vulcanized product. In addition, a vulcanized product forcompression set test was prepared by heating at 160° C. at 100 kg/cm²for 20 minutes.

EXAMPLES 2 TO 4 AND COMPARATIVE EXAMPLE 1

A sheet-like rubber composition for vulcanization was obtained in thesame manner as in Example 1 except that the blending materials shown inTable 1 were used in ratios shown in Table 1, and further a vulcanizedrubber was obtained.

EXAMPLES 5 TO 8

By using the blending materials shown in Table 2 in ratios shown inTable 2, a reinforcing agent, a plasticizer, and an acid receiving agent(a) were added to chlorinated polyethylene, followed by kneading themixture at 130° C. in Example 5, at 150° C. in Example 6, at 170° C. inExample 7, and at 190° C. in Example 8 for 6 minutes, by means of akneader. Then, a vulcanizing agent and an organic vulcanizationaccelerator were added to the kneaded product, followed by furtherkneading the whole mixture by means of a roll heated to 70 to 80° C.Thereafter, the same operations as in Example 1 were carried out to givea sheet-like rubber composition for vulcanization, and further avulcanized rubber was obtained.

EXAMPLES 9 AND 10

By using the blending materials shown in Table 2 in ratios shown inTable 2, a sheet-like rubber composition for vulcanization was obtainedin the same manner as in Example 1 except that a synthetic zeolite (I)activated by calcination under a nitrogen stream at 200° C.×30 minuteswas used as an acid receiving agent, and further a vulcanized rubber wasobtained.

EXAMPLES 11 TO 13

A sheet-like rubber composition for vulcanization was obtained in thesame manner as in Example 8 except that the blending materials shown inTable 3 were used in ratios shown in Table 3, and further a vulcanizedrubber was obtained.

The blending materials, the blending ratios thereof, and the kneadingtemperature (the temperature in kneading a mixture with no vulcanizingagent and with no organic vulcanization accelerator) used in Examplesand Comparative Examples are shown in Tables 1 to 3.

EXAMPLES 14 TO 16 AND COMPARATIVE EXAMPLES 2 TO 3

A composition for vulcanization and a vulcanized product were obtainedin the same manner as in Example 1 by using the compounding agents shownin Table 4 and adding a different thiadiazole vulcanizing agent.

EXAMPLES 17 TO 24

A composition for vulcanization and a vulcanized product were obtainedin the same manner as in Example 1 by using the compounding agents shownin Table 5 and changing the kind of the inorganic vulcanizationaccelerator.

EXAMPLES 25 TO 30 AND COMPARATIVE EXAMPLE 5

A white composition for vulcanization and a white vulcanized productwere obtained in the same manner as in Example 1 by using thecompounding agents shown in Table 6 and adding a white filler or aninorganic vulcanization accelerator.

EXAMPLE 31 AND COMPARATIVE EXAMPLE 6

A composition for vulcanization and a vulcanized product were obtainedin the same manner as in Example 1 by using the compounding agents shownin Table 7 and using an epichlorohydrin polymer as thechlorine-containing polymer. The heating to obtain the vulcanizedproduct was carried out at 170° C.

EXAMPLES 32 TO 35

A sheet-like rubber composition for vulcanization of chlorinatedpolyethylene having a thickness of 2 to 3 mm was prepared in the samemanner as in Example 1 by using the compounding agents shown in Table 9.

A sheet-like rubber composition for vulcanization made of a blend ofacrylonitrile butadiene polymer/polyvinyl chloride (hereafter referredto as NBR/PVC) shown in Table 8 and a sheet-like rubber composition forvulcanization made of epichlorohydrin (hereafter referred to as ECO)were prepared.

The sheet-like NBR/PVC rubber composition for vulcanization or thesheet-like ECO rubber composition and a sheet-like rubber compositionfor vulcanization of chlorinated polyethylene of this Example weresuperposed. This superposed product was press-bonded at 80° C. for 100kg/cm² for 5 minutes, followed by steam vulcanization at 160° C. for 20minutes to give a vulcanized laminated product.

EXAMPLES 36 TO 38 AND COMPARATIVE EXAMPLES 7 TO 8

A composition for vulcanization and a vulcanized product were obtainedin the same manner as in Example 1 by using the compounding agents shownin Table 10 and using chlorosulfonated polyethylene as thechlorine-containing polymer.

EXAMPLES 39 TO 41 AND COMPARATIVE EXAMPLE 9

A composition for vulcanization and a vulcanized product were obtainedin the same manner as in Example 1 by using the compounding agents shownin Table 11 and using an epichlorohydrin polymer as thechlorine-containing polymer. The heating to obtain the vulcanizedproduct was carried out at 170° C.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1Chlorinated polyethylene 100 100 100 100 100 Reinforcing agent 60 60 6060 60 Plasticizer I 30 30 30 30 30 Acid receiving agent I 2 5 10 20 Acidreceiving agent III 10 Vulcanizing agent I 1.25 1.25 1.25 1.25 1.25Organic vulcanization accelerator I 2.5 2.5 2.5 2.5 2.5 Kneadingtemperature (° C.) 130 130 130 130 130 parts by weight

TABLE 2 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10Chlorinated polyethylene 100 100 100 100 100 100 Reinforcing agent 60 6060 60 60 60 Plasticizer I 30 30 30 30 30 30 Acid receiving agent I 10 1010 10 (calcination) 10 (calcination) 10 Vulcanizing agent I 1.25 1.251.25 1.25 1.25 1.25 Organic vulcanization accelerator I 2.5 2.5 2.5 2.52.5 2.5 Kneading temperature (° C.) 130 150 170 190 130 190 parts byweight

TABLE 3 Example Example Example 11 12 13 Chlorinated polyethylene 100100 100 Reinforcing agent 60 60 60 Plasticizer I 30 30 30 Acid receivingagent I 10 10 Acid receiving agent II 10 Vulcanizing agent I 1.25 — 1.25Vulcanizing agent II — 1.25 — Organic vulcanizing accelerator I 2.5 2.5— Organic vulcanizing accelerator II — — 0.9 Kneading temperature (° C.)190 190 190 parts by weight

TABLE 4 Comparative Comparative Comparative Example 2 Example 14 Example3 Example 15 Example 4 Example 16 Chlorinated polyethylene 100 100 100100 100 100 Reinforcing agent 60 60 60 60 60 60 Plasticizer I 35 35 3535 35 35 Lubricant 2 2 2 2 2 2 Acid receiving agent III 10 — 10 — 10 —Acid receiving agent I — 10 — 10 — 10 Vulcanizing agent III 2 2 — — — —Vulcanizing agent IV — — 2.53 2.53 — — Vulcanizing agent V — — — — 4 4Organic vulcanization accelerator III 1.5 1.5 1.5 1.5 1.5 1.5 Inorganicvulcanization accelerator I — — — 2 — 2 parts by weight

TABLE 5 17 18 Example 19 Example 20 Example 21 Example 22 Example 23Example 24 Chlorinated polyethylene 100 100 100 100 100 100 100 100Reinforcing agent 60 60 60 60 60 60 60 60 Plasticizer I 35 35 35 35 3535 35 35 Lubricant 2 2 2 2 2 2 2 2 Acid receiving agent I 10 10 10 10 1010 10 10 Vulcanizing agent III 2 2 2 2 2 2 2 2 Organic vulcanizationaccelerator III 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Inorganic vulcanizationaccelerator II — 2 — — — — — — Inorganic vulcanization accelerator III —— 2 — — — — — Inorganic vulcanization accelerator IV — — — 2 — — — —Inorganic vulcanization accelerator I — — — — 0.5 1 2 4 parts by weight

TABLE 6 Comparative Example 5 Example 25 Example 26 Example 27 Example28 Example 29 Example 30 Chlorinated polyethylene 100 100 100 100 100100 100 White filler I 80 80 — — — White filler II — — 80 — — 60 40White filler III — — — 80 — Inorganic vulcanization accelerator II — — —— 80 Inorganic vulcanization accelerator V 10 20 Plasticizer I 35 35 3535 35 35 35 Lubricant 2 2 2 2 2 2 2 Acid receiving agent III 10 — — — —Acid receiving agent I 10 10 10 10 10 10 Vulcanizing agent III 2 2 2 2 22 2 Organic vulcanization accelerator III 1.5 1.5 1.5 1.5 1.5 1.5 1.5Inorganic vulcanization accelerator I 2 2 2 2 2 2 2 parts by weight

TABLE 7 Comparative Example 6 Example 31 Epichlorohydrin polymer 100 100Reinforcing agent 50 50 Plasticizer II 10 10 Lubricant 2 2 Anti-agingagent 1 1 Acid receiving agent III 10 — Acid receiving agent I — 10Vulcanizing agent III 1.5 1.5 parts by weight

TABLE 8 parts by weight NBR/PVC rubber composition NBR/PVC 100Reinforcing agent 90 Plasticizer III 15 stearic acid 1 Anti-aging agent1 Zinc white 5 Organic vulcanization accelerator VI 1 Organicvulcanization accelerator VII 0.5 Sulfur 0.5 ECO rubber compositionEPICHLOMER C 100 Reinforcing agent 50 Plasticizer III 20 White carbon 10Light calcium carbonate 15 Anti-aging agent 1 Lubricant 1.5 Organicvulcanization accelerator VIII 1 Calcium hydroxide 1.5 Vulcanizing agentVII 1.5

TABLE 9 Example 32 Example 33 Example 34 Example 35 Chlorinatedpolyethylene 100 100 100 100 White filler II 80 80 80 80 Plasticizer I35 35 35 35 Lubricant 2 2 2 2 Acid receiving agent I 10 10 10 10Vulcanizing agent III 2 2 2 2 Organic vulcanization accelerator III 3 —— — Organic vulcanization accelerator IV — 1.2 — — Organic vulcanizationaccelerator I — — 2.4 — Organic vulcanization accelerator V — — — 1.3Inorganic vulcanization accelerator II — 2 — 2 parts by weight

TABLE 10 Comparative Comparative Example 7 Example 36 Example 37 Example8 Example 38 Chlorosulfonated polyethylene 100 100 100 100 100Reinforcing agent 60 60 60 — — White filler II — — — 80 80 Plasticizer I35 35 35 35 35 Lubricant 2 2 2 2 2 Acid receiving agent III 10 — — 10 —Acid receiving agent I — 10 10 — 10 Inorganic vulcanization acceleratorII — — 2 — 2 Vulcanizing agent VI 2 2 2 2 2 Organic vulcanizationaccelerator IX 1 1 1 1 1 parts by weight

TABLE 11 Comparative Example Example Example Example 9 39 40 41Epichlorohydrin 100 100 100 100 polymer Reinforcing agent 50 50 50 50Plasticizer II 10 10 10 10 Lubricant 3 3 3 3 Anti-aging agent 1 1 1 1Acid receiving 3 — — — agent III Acid receiving agent I — 5 10 10Anti-scorching agent 1 1 1 1 Vulcanizing agent I 1.2 1.2 1.2 — Organicvulcanization 0.5 0.5 0.5 — accelerator X Vulcanizing agent VII — — —1.7 parts by weight

Performance Test

In the Examples and Comparative Examples, the chlorinated polyethylenevulcanizing composition immediately after the kneading was subjected tothe Mooney Scorch test as prescribed by JIS K6300 (physical test methodfor non-vulcanized rubber) to give the Vm value (125° C.). Then thecomposition was subjected to the Mooney Scorch test after it was left tostand for 3 days or 7 days at 35° C. under humidity of 75% after thekneading to give the Vm value (125° C.). The difference (ΔVm) of theseVm values was determined.

Also, physical property tests were carried out on the obtainedvulcanized products according to JIS K6251 (tensile test method forvulcanized rubber), JIS 6253 (hardness test method for vulcanizedrubber) and JIS K6262 (compression set test method for vulcanizedrubber).

The obtained test results are shown in Tables 12 to 21.

Laminated products of Examples 32 to 35 were cut into 1 cm in width, anda peeling test was carried thereon according to JIS K6256 (adhesion testmethod for vulcanized rubber). In the Table 19, the term “CPEdestruction” for representing a peeled state of the peeling test meansthat a rubber destruction occurred at the chlorinated polyethyleneportion.

TABLE 12 Example 1 Example 2 Example 3 Example 4 Comparative Example 1Mooney scorch 125° C. Vm 55.5 50.8 53.1 52.3 61.8 t₅ (min) 7.0 7.4 7.27.1 7.4 preservation stability (3 days) Δ Vm +2 +1 +2 +4 +17 t₅ (min)7.1 6.7 6.9 7.5 19.5 initial physical properties M₁₀₀ (MPa) 3.3 3.3 4.04.3 5.2 M₃₀₀ (MPa) 12.5 12.5 14.0 14.8 17.9 Tb (MPa) 19.7 19.8 19.8 18.921.3 Eb (%) 535 510 470 415 390 Hs (JIS A) 67 66 68 71 69 compressionset (%) 49 46 43 36 38

TABLE 13 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10Mooney scorch 125° C. Vm 50.2 53.3 52.5 53.6 54.1 54.1 t₅ (min) 7.8 7.77.7 7.9 7.5 7.6 preservation stability (7 days) Δ Vm +3 +2 +1 0 +2 +1 t₅(min) 7.5 7.5 7.3 7.1 7.4 7.1 initial physical properties M₁₀₀ (MPa) 4.14.9 4.8 4.9 5.2 6.2 M₃₀₀ (MPa) 13.0 14.0 14.5 15.0 14.7 17.2 Tb (MPa)16.5 17.2 17.3 17.4 17.2 18.1 Eb (%) 450 450 420 395 395 335 Hs (JIS A)70 71 72 74 74 73 compression set (%) 48 46 46 42 42 33

TABLE 14 Example 11 Example 12 Example 13 Mooney scorch 125° C. Vm 65.258.9 65.8 t₅ (min) 7.1 5.1 6.6 Preservation stability (3 days) Δ Vm −1 0+1 t₅ (min) 6.6 6.9 7.5 initial physical properties M₁₀₀ (MPa) 4.7 5.54.4 M₃₀₀ (MPa) 14.9 14.5 14.3 Tb (MPa) 17.9 15.3 17.4 Eb (%) 425 335 425Hs (JIS A) 71 75 68 compression set (%) 43 35 40

TABLE 15 Example Comparative Example 2 Example 14 Comparative Example 3Example 15 Comparative Example 4 16 Mooney scorch 125° C. Vm  60   45 64    54    62    54   t₅ (min)  8.5 13.1  7.8  14.4  8.4  11.9preservation stability (3 days) Vm   200<  56   200<   75     200<  74   Δ Vm (points) +11  +21    +20   t₅ (min) 13.9 30<   30<  initialphysical properties M₁₀₀ (MPa)  5.7 3.4  4.4  3.8  4.6  4.2 M₃₀₀ (MPa) 14.9 10.3  13.7  11.5  13.4  12.7 Tb (MPa)  15.7 14.2  15.7  14.5  15.2 14. 8 Eb (%) 325   500 365   420   365   390   Hs (JIS A)  71   69 74    74    75    75   compression set (%)  20   63  34    44    37   41  

TABLE 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example22 Example 23 Example 24 Mooney scorch 125° C. Vm 49 44 45 46 45 46 4645 t₅ (min) 12.4 12.4 13.1 14.0 15.5 14.5 13.9 17.1 preservationstability (3 days) Vm 60 65 66 61 64 65 67 62 Δ Vm (points) +11 +21 +21+15 +19 +19 +21 +17 t₅ (min) 20.1 6.6 10.2 8.4 8.8 8.7 15.1 24.4 initialphysical properties M₁₀₀ (MPa) 3.2 5.6 4.0 4.4 3.9 4.7 4.5 4.6 M₃₀₀(MPa) 9.6 14.2 11.3 11.7 10.6 11.9 12.3 11.6 Tb (MPa) 13.9 15.8 14.514.6 14.2 13.6 15.3 14.2 Eb (%) 560 365 445 420 490 370 410 410 Hs (JISA 67 72 69 75 72 73 74 74 compression set (%) 71 25 39 43 61 41 32 38

TABLE 17 Comparative Example 5 Example 25 Example 26 Example 27 Example28 Example 29 Example 30 Mooney scorch 125° C. Vm 31 26 23 32 26 29 31t₅ (min) 11.2 21.5 18.5 15.9 18.9 15.6 9.5 preservation stability (3days) Vm 62 30 27 39 33 37 47 Δ Vm (points) +31 +4 +4 +7 +7 +8 +16 t₅(min) 4.5 10.4 10.8 10.6 10.5 7.0 6.2 initial physical properties M₁₀₀(MPa) 2.9 2.9 3.3 2.0 1.0 2.9 2.5 M₃₀₀ (MPa) 3.7 3.5 3.9 3.6 1.8 3.8 4.3Tb (MPa) 12.8 6.6 10.8 10.5 9.1 10.5 13.4 Eb (%) 700 710 710 575 505 640565 Hs (JIS A 70 62 69 63 57 68 67 compression set (%) 48 38 71 52 46 6848

TABLE 18 Comparative Example 6 Example 31 Mooney scorch 125° C. Vm  51  48 t₅ (min)  10.0 14.5 preservation stability (3 days) Vm  200<  72 Δ Vm(points) — +24 t₅ (min) — 5.8 initial physical properties M₁₀₀ (MPa) 2.6 1.5 M₃₀₀ (MPa)  6.6 3.3 Tb (MPa)  12.7 8.1 Eb (%) 860   955 Hs (JISA  67   65 compression set (%)  66   85

TABLE 19 Example 32 Example 33 Example 34 Example 35 Mooney scorch l25°C. Vm 26 28 27 17 t₅ (min) 14.2 10.0 18.6 14.0 preservation stability (3days) Vm 27 38 38 24 Δ Vm (points) +1 +10 +11 +7 t₅ (min) 7.5 7.5 6.86.4 initial physical properties M₁₀₀ (MPa) 3.6 2.4 2.7 2.2 M₃₀₀ (MPa)5.0 2.7 3.0 2.5 Tb (MPa) 9.8 11.3 11.1 7.8 Eb (%) 475 825 795 875 Hs(JIS A 69 63 66 64 compression set (%) 37 45 59 43 Peeling from NBR/PVCpeel strength (kg/cm) 2.6 2.5 3.5 2.4 peeled state CPE CPE CPE CPEdestruction destruction destruction destruction Peeling from ECO peelstrength (kg/cm) 2.5 2.3 3.4 2.5 peeled state CPE CPE CPE CPEdestruction destruction destruction destruction

TABLE 20 Comparative Example 7 Example 36 Example 37 Comparative Example8 Example 38 Mooney scorch 125° C. Vm 24.4  18    17   11.7  10   t₅(min) 12.5   30<    30<  24.2   30<  preservation stability (3 days) Vm43.2  19    17.3 19.2  10.8 Δ Vm (points) +19  +1    0   +7  +1   t₅(min) 5.5  27.6  16.8 7.2  24.8 initial physical properties M₁₀₀ (MPa)4.5  2.8  4.2 4.8  2.5 M₃₀₀ (MPa) 15.2  11    15.7 5.9  3.5 Tb (MPa)17.5  14.6  17.1 13.6  14.6 Eb (%) 345 475   350   685 765   Hs (JIS A)67  66    70   67  61   compression set (%) 82  84    74   88  88  

TABLE 21 Comparative Example 9 Example 39 Example 40 Example 41 Mooneyscorch 125° C. Vm 38 40 39 41 t₅ (min) 24.0 18.0 12.8 44.0 preservationstability (3 days) Vm 52 38 44 37 Δ Vm (points) +14 −2 +5 −4 t₅ (min)9.8 15.3 8.6 24.0 initial physical properties M₁₀₀ (MPa) 3.0 1.5 2.0 1.3M₃₀₀ (MPa) 7.5 3.8 5.1 2.9 Tb (MPa) 11.6 10.5 11.6 6.6 Eb (%) 615 955845 710 Hs (JIS A) 67 60 63 67 compression set (%) 44 67 54 83

In the above Tables, t₅ represents a Mooney Scorch time as defined inthe Mooney Scorch test of JIS K6300; M₁₀₀ represents a tensile stress at100% elongation as defined in the tensile test of JIS K6251; M₃₀₀represents a tensile stress at 300% elongation as defined in the tensiletest of JIS K6251; T_(b) represents a tensile strength as defined in thetensile test of JIS K6251; E_(b) represents an elongation as defined inthe tensile test of JIS K6251; H_(s) represents a hardness as defined inthe hardness test of JIS K6253; and the “compression set” represents acompression set ratio (%) as defined in the compression set test of JISK6262, where the compression ratio is 25%, the heat treating temperatureis 100° C., and the heat treating time is 72 hours. In the Tables 18 and21, the heat treating temperature is 125° C.

As understood from the above Tables, the preservation stability of thevulcanizing composition increased greatly by blending a zeolite compoundas an acid receiving agent.

In Examples 5 to 8, in which all the blending materials except thevulcanizing agent (b) and the organic vulcanization accelerator (c) arekneaded at the same time, the preservation stability is kept good andthe vulcanization physical properties, especially M₁₀₀, and thecompression set are further improved with the rise of the kneadingtemperature.

In Examples 9 and 10 using an activated synthetic zeolite, thepreservation stability is kept good and the vulcanization physicalproperties, especially M₁₀₀, and the compression set are furtherimproved with the rise of the kneading temperature.

The vulcanizing compositions of Comparative Examples 2 to 4 usingconventionally known MgO have a very poor preservation stability whereasthe vulcanizing compositions of Examples 14 to 16 containing a syntheticzeolite as an acid receiving agent have an excellent preservationstability.

In Examples 17 to 24, the vulcanization speed increases and,particularly the compression set property is greatly improved by addingan inorganic vulcanization accelerator. In Examples 18 to 24, even avery small amount of addition of an inorganic vulcanization acceleratorbrings about the advantageous effect.

Examples 25 to 30 are those using a white filler or an inorganicvulcanization accelerator. In Comparative Example 5 the preservationstability is poor whereas in Example 25 using a synthetic zeolite, thepreservation stability is very good. Examples 26 to 30 using a whitefiller or an inorganic vulcanization accelerator exhibit a goodpreservation stability.

In Examples 32 to 35 a vulcanized laminated product having a largepeeling strength is obtained. Since the scorching time is sufficientlylong and the preservation stability is good, a hose made of thisvulcanized laminated product has a large peeling strength and can bemolded by extrusion without troubles.

A good preservation stability was exhibited also in Examples 31, 39, 40,and 41, where epichlorohydrin rubber was used as the chlorine-containingpolymer, and in Examples 36 to 38, where chlorosulfonated polyethylenewas used as the chlorine-containing polymer.

According to the present invention, the preservation stability of achlorine-containing polymer vulcanizing composition can be greatlyimproved by incorporating blending a zeolite compound as an acidreceiving agent.

In addition, the preservation stability is kept good and thevulcanization physical properties are further improved with the rise ofthe kneading temperature by using an activated zeolite compound as azeolite compound.

What is claimed is:
 1. A chlorine-containing polymer vulcanizingcomposition obtained by blending (a) a zeolite composition; (b) avulcanizing agent selected from the group consisting of a2,3-dimercaptoquinoxaline derivative, a thiourea compound, and a thiuramcompound: and (c) an organic vulcanization accelerator; with achlorine-containing polymer, wherein said chlorine-containing polymer isa polymer selected from the group consisting of chlorinatedpolyethylene, epichlorohydnn polymer, polyvinyl chloride, chloroprenerubber, chlorinated natural rubber, chlorosulfonated polyethylene,chlorinated butyl rubber, and acrylic rubber copolymerized with achlorine-containing monomer, or a mixture thereof, and wherein saidorganic vulcanization accelerator is a compound selected from the groupconsisting of a primary amine, a secondary amine, a tertiary amine, anorganic acid salt or adduct of said amine, an aldehyde ammonia compound,an aldehyde amine compound, a guanidine compound, a thiazole compound, asulfeneamide compound, a thiuram compound, a dithocarbamic acidcompound, 1,8-diazabicvclo(5,4,0)undecene-7, and a weak acid saltthereof, and a quaternary ammonium salt compound, or a mixture thereof.2. A chlorine-containing polymer vulcanizing composition according toclaim 1, wherein said chlorine-containing polymer is a blend of achlorine-containing polymer in a major proportion and another rubberand/or resin in a minor proportion.
 3. A chlorine-containing polymervulcanizing composition according to claim 1, wherein said zeolitecompound is a polymer selected from the group consisting of naturalzeolite, an A-type synthetic zeolite, X-type synthetic zeolite, Y-typesynthetic zeolite, a sodalite, natural or synthetic mordenite, ZSM-5,and a metal substitution product thereof, or a mixture thereof.
 4. Achlorine-containing polymer vulcanizing composition according to claim3, wherein said zeolite compound is an activated zeolite compound.
 5. Achlorine-containing polymer vulcanizing composition according to claim1, wherein (a) 0.5 to 30 parts by weight of said zeolite compound, (b)0.1 to 5 parts by weight of said vulcanizing agent, and (c) 0.5 to 3 molof said organic vulcanization accelerator with respect to 1 mol of (b)said vulcanizing agent are blended with 100 parts by weight ofchlorinated polyethylene.
 6. A chlorine-containing polymer vulcanizingcomposition according to claim 1, wherein (a) 0.5 to 30 parts by weightof said zeolite compound, (b) 0.1 to 5 parts by weight of saidvulcanizing agent, and (c) 0.5 to 3 mole of said organic vulcanizationaccelerator with respect to 1 mol of (b) said vulcanizing agent areblended with 100 parts by weight of an epichlorohydrin polymer.
 7. Achlorine-containing polymer vulcanizing composition according to claim1, wherein (a) 0.5 to 30 parts by weight of said zeolite compound, (b)0.1 to 5 parts by weight of said vulcanizing agent, and (c) 0.5 to 3 molof said organic vulcanization accelerator with respect to 1 mol of (b)said vulcanizing agent are blended with 100 parts by weight ofchlorosulfonated polyethylene.
 8. A chlorine-containing polymervulcanizing composition according to claim 1, wherein (a) 0.5 to 30parts by weight of said zeolite compound, (b) 0.1 to 5 parts by weightof said vulcanizing agent, (c) 0.5 to 3 mol of said organicvulcanization accelerator with respect to 1 mol of said vulcanizingagent, and further (d) 0 to 20 parts by weight of an inorganicvulcanization accelerator are blended with 100 parts by weight of achlorine-containing polymer.
 9. A chlorine-containing polymervulcanizing composition according to claim 8, wherein said inorganicvulcanization accelerator is a compound selected from the groupconsisting of a basic metal oxide, a basic metal salt, a basic metalhydroxide, a basic silicon dioxide, a silicate, and a hydrotalcite. 10.A chlorine-containing polymer vulcanizing composition according to claim8, wherein said inorganic vulcanization accelerator is a basic metalcarbonate, and said chlorine-containing polymer is chlorinatedpolyethylene or an epichlorohydrin polymer.
 11. A chlorine-containingpolymer vulcanized product obtained by vulcanizing a chlorine-containingpolymer vulcanizing composition according to claim
 1. 12. A laminatedproduct comprising a layer of epichlorohydrin rubber, nitrile rubber,nitrile rubber containing polyvinyl chloride blended therewith, oracrylic rubber, and a layer of a chlorine-containing polymer vulcanizedproduct according to claim
 11. 13. A laminated hose comprising an innerlayer of epichlorohydrin rubber, nitrile rubber, nitrile rubbercontaining polyvinyl chloride blended therewith, or acrylic rubber, andan outer layer of a chlorine-containing polymer vulcanized productaccording to claim
 11. 14. A chlorine-containing polymer vulcanizingcomposition consisting of: a zeolite compound; a vulcanizing agentselected from the group consisting of a 2,3-dimercaptoquinoxalinederivative, a thiourea compound, and a thiuram compound; an organicvulcanization accelerator selected from the group consisting of aprimary amine, a secondary amine, a tertiary amine, an organic acid saltor adduct of said amine, an aldehyde ammonia compound, an aldehyde aminecompound, a guanidine compound, a thiazole compound, a sulfeneamidecompound, a thiuram compound, a dithocarbamic acid compound,1,8-diazabicyclo(5,4,0)undecene-7, and a weak acid salt thereof, and aquaternary ammonium salt compound, or a mixture thereof; and achlorine-containing polymer selected from the group consisting ofchlorinated polyethylene, epichlorohydrin polymer, polyvinyl chloride,chloroprene rubber, chlorinated natural rubber, chlorosulfonatedpolyethylene, chlorinated butyl rubber, and acrylic rubber copolymerizedwith a chlorine-containing monomer, or a mixture thereof.